When painting a portrait, I like to begin with the eyes. After painting in the whites with a slightly purple hue, I colour in the iris (in my case, a hazel colour) then the dark pupil, using a mix of Ultramarine Blue and Scarlet. To set the eye into the socket, you need to deal with it in the same way as a ball - shadow around the edges of the white and up under the eyelid. A lighter hazel colour can then be added onto the iris for highlights leaving a darker ring around the edge. At this stage, I don't worry about eyelashes until after I have some flesh tones painted in.
For flesh tones, I am using a Scarlet, Cadmium Lemon and Pthalo Green with Ultramarine Blue added for any shadows. Mix the Scarlet and Lemon first, slowly adding the Green, which is a very strong colour. This is my base colour - by adding white, I have a highlight. With the same base colour you can add the Ultramarine Blue and extra Scarlet for a rich shadow colour. Once these three colours are mixed on the palette, I can work quickly over the whole face, using the base colour, highlights and shadows where needed. Then I can go back into the face and start on detail.
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